CN1170796C - 羧酸、酸酐或其酯经氢化制醇的工艺 - Google Patents
羧酸、酸酐或其酯经氢化制醇的工艺 Download PDFInfo
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- CN1170796C CN1170796C CNB988119765A CN98811976A CN1170796C CN 1170796 C CN1170796 C CN 1170796C CN B988119765 A CNB988119765 A CN B988119765A CN 98811976 A CN98811976 A CN 98811976A CN 1170796 C CN1170796 C CN 1170796C
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- Prior art keywords
- hydrogenation
- technology
- catalyst
- copper
- catalyzer
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- 238000005984 hydrogenation reaction Methods 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 238000005516 engineering process Methods 0.000 claims description 16
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
一种将羧酸、酸酐或其酯在包含或者由元素周期表6、7、8、9、10和11族以及，如果适宜的话，2、14和15族的氢化元素构成的异相催化剂上，在液相中于100～300℃和10～300bar催化氢化成醇的工艺，其包含向氢化反应混合物中添加基于液体氢化原料1～3000ppm的碱性碱金属化合物或碱土金属化合物，其选择自氢氧化物、碳酸盐、羧酸盐和醇盐。
Description
本发明涉及一种向氢化原料中添加特定的碱性的碱金属化合物或碱土金属化合物，借以在羧酸或其衍生物的氢化反应过程中提高催化剂活性并防止二次反应的工艺。
已知的是，在氢化催化剂的制备过程中用到了碱性组分。而这些组分或多或少地留存在最终的催化剂上。比如，EP-A 528 305描述了Cu/ZnO/Al2O3催化剂的制备，其中在催化剂成份沉淀过程中使用了碱性化合物如碱金属碳酸盐、碱金属氢氧化物或碱金属碳酸氢盐。少量的碱金属添加剂于是就残留在催化剂当中。制备含碱金属催化剂的另一个例子可参见DE-A 2 321 101，其中制备的是含Co的催化剂。EP-A 552 463描述了Cu/Mn/Al催化剂的制备，鉴于制备方法之故，其同样也含有少量的碱金属。
得到的氢化催化剂含有在整个催化剂组份之中均匀分散的碱金属。但是，因为只有催化剂的外露或可接触的表面才具备催化活性，所以这些位置上的碱金属的量很少而且由于碱金属并非共价键合，而是仅以松散结合的形式存在，所以一般很快就被待氢化物料冲走。除此之外，引入能使催化剂酸化的化合物，将会迅速耗尽碱金属形成的碱性中心的容量。结果是，为酸性催化剂所加速的醚化或脱水等反应，会降低氢化成醇的选择性。一般来讲，引入使催化剂酸化的化合物，有时会大大降低催化剂的使用寿命，因为催化剂的表面结构发生了变化，比如源自催化剂成份被洗脱或活性金属的重结晶。
因此，氢化催化剂有时对氢化原料本身或者是原料氢或氢化原料中所含的杂质很敏感。因此在羧酸氢化反应过程中，许多催化剂，比如不仅被酸化了而且还会因催化剂成份的洗脱，从化学结构上遭到严重的破坏。即使原材料中不含任何羧酸，但是比方说含酯，那么酯一般就会受痕量水的作用而水解释放出羧酸。另一个问题是关于杂质的，比如有机卤化物，它可能比如随氢而夹带到氢化反应中来，并且会产生不利的影响，即使是在这些物质的含量小于1ppm的情况下。因此已知的是，比如可借Cu催化剂经化学吸附而从原始物料中除去痕量的卤素(US 5,614,644)。如果不这样预吸附的话，卤素就会吸附在氢化催化剂上，于其处首先造成酸化并随后改变催化剂的结构。
因此，工业上对所述问题的解决办法典型地包含在上游物料中设置一个“看门垫”，有害杂质在其中得到吸收。这当然无法除去于反应过程有关的酸，比如生成的或用作氢化原料的羧酸。
本发明的目的是提供一种工艺，借以降低或消除于反应有关的酸以及引入杂质对催化剂的毒害作用。
我们发现借助一种工艺就能达到此目的，一种将羧酸、酸酐或其酯在包含或者由元素周期表6、7、8、9、10和11族以及，如果适宜的话，2、14和15族的氢化元素构成的异相催化剂上，在液相中于100～300℃和10～300bar催化氢化成醇的工艺，其包含向氢化反应混合物中添加基于液体氢化原料为1～3000ppm，特别是3～1000ppm，优选5～600ppm的碱性碱金属化合物或碱土金属化合物，其选择自氢氧化物、碳酸盐、羧酸盐和醇盐。
DE 1 235 879在实施例16中公开了向氢化原料中添加磷酸三钠。此实施例描述了一种羧酸混合物的氢化过程，其包含0.1wt％的Na3PO4，以及特别有己二酸、戊二酸、丁二酸和6-羟基己酸，己氢化的羧酸混合物还及含水量调至7％的未知量“粗一元醇”。然而，仅向氢化物料中添加Na3PO4对提高催化剂活性和使用寿命而言并不是一个好办法。由于反应混合物中酸化成份的存在，活性没过多久就会急剧下降。
羧酸及衍生物可能是羧酸本身及酯，也可能是内环酯，即内酯，以及酸酐。例子是乙酸酯、丙酸酯、己酸酯、十二烷酸酯、十五烷酸酯、十六烷酸酯、2-环十二烷基丙酸酯、脂肪酸甘油酯、马来酸二酯、琥珀酸二酯、富马酸二酯、戊二酸二酯、己二酸二甲酯、6-羟基己酸酯、环己烷二酸二酯、苯甲酸酯、丁内酯、己内酯、马来酸、琥珀酸、衣康酸、己二酸、6-羟基己酸、环己烷二酸、苯甲酸、马来酸酐和琥珀酸酐。优选的起始物是二酯，特别是4～6个碳原子二羧酸的低分子醇二酯。因此，优选地，本发明的工艺包含将4～6个碳原子的二羧酸、酸酐或其酯氢化成相应的二醇。
适宜的碱性化合物尤其是碱金属氢氧化物和碱土金属氢氧化物，比如LiOH、NaOH、KOH、RbOH、CsOH、Mg(OH)2、Sr(OH)2或Ba(OH)2。也可以是碱金属或碱土金属的羧酸盐形式，比如甲酸盐、乙酸盐、丙酸盐、马来酸盐或戊二酸盐，或者醇盐如甲醇盐、乙醇盐或丙醇盐。碳酸盐也是适宜的。例如，碱性碱金属化合物是碱性的钠或钾化合物。碱性化合物在液体氢化原料中总能均匀溶解。如果不能保证如此的话，碱性化合物也可处于适当的溶剂中以单独物料的形式添加到氢化反应本身或液体氢化原料中去。碱金属或碱土金属的量极低，为1～3000ppm，优选3～1000ppm，特别优选5～600ppm，基于液体氢化原料。碱性化合物优选连续添加。虽然分批添加也是可能的。基于液体氢化原料，氢化反应中引入的碱性化合物的量在短时间内高于3000ppm也是可能的。但平均而言，量要低于3000ppm。
令人惊奇的是，即使是在碱性化合物长时间添加的情况下，催化剂上也不见沉积。
氢化反应在液相中发生。对于固定床催化剂而言，选择的是上行还是下行的流动方法并不重要。以悬浮催化剂进行氢化反应也是可能的。
本新型工艺中所用的氢化反应催化剂一般是适于羰基氢化的异相催化剂。其例可参见Houben-Weyl，Methoden der OrganischenChemie，Vol.IV/1c，pp.16～26。
在这些氢化反应催化剂当中，优选其包含元素周期表中6、7、8、9、10和11族以及，如果适宜的话，2、14和15族的一个或多个元素，特别是铜、铬、铼、钴、铑、镍、钯、铁、铂、铟、锡和锑。特别优选含有铜、钴、钯、铂或铼的催化剂。
适宜的催化剂尤其是非承载型催化剂。在绝大多数情况下，催化活性的金属不处于载体物上。其例是Raney催化剂，比如基于Ni、Cu或钴。其它例子是钯黑、铂黑、海绵铜，比如Pd/Re、Pt/Re、Pd/Ni、Pd/Co或Pd/Re/Ag的合金或混合物。
新型工艺中所用的催化剂也可以，比如是沉淀型催化剂。这种类型催化剂的制备是，通过比如添加碱金属氢氧化物和/或碱土金属氢氧化物和/或碱金属碳酸盐和/或碱土金属碳酸盐的溶液，比如以微溶氢氧化物、水合氧化物、碱式盐或碳酸盐的形式从其盐溶液，特别是从其硝酸盐和/或乙酸盐溶液中沉淀出具备催化活性的组份，然后干燥得到的沉淀物，接着一般在300～700℃、特别是400～600℃经煅烧转变成相应的氧化物、氧化混合物和/或价键氧化混合物，一般在50～700℃、特别是在100～400℃下以氢或含氢气体进行处理，将其还原形成相应的金属和/或低氧化态的氧化物并转变成具备真正催化活性的形式。此还原反应一般进行到不再有水生成为止。为了制备包含有载体物的沉淀型催化剂，催化活性组份可在相应载体物的存在下沉淀。但是，催化活性组份与载体物从相关盐溶液中同时沉淀也是可取的。为本新型工艺优选的氢化反应催化剂包含沉积在载体物上的氢化反应催化性金属或金属混合物。除了上述的沉淀型催化剂以外，它除了催化活性组分还包含一种载体物，于本新型工艺适用的载体物一般是，其中起氢化反应催化作用的组份已经比如借浸渍法施用在载体物上。
以何种方式将催化活性金属施用到载体上一般并没有严格限制，而且可借多种方法实现。催化活性金属可借此方法施用到载体物上，比如以相应元素的盐或氧化物的溶液或悬浮体浸渍、干燥并随后经还原剂，优选选用氢或混合氢化物，将金属化合物还原成相应的金属或低氧化态的化合物。将催化活性金属施用到载体上的另一种可能的途径是，以易于热分解的盐溶液如硝酸盐或者是易于热分解的配位化合物如催化活性金属的羰基或氢化配合物浸渍载体，并将按此方式浸渍的载体加热到300～600℃，以使吸附的金属化合物热分解。热分解过程优选在保护性气体的气氛下进行。适宜的保护性气体的例子是氮气、二氧化碳、氢和惰性气体。催化活性金属也可借蒸汽沉积法或火焰喷射法沉积在催化剂载体上。催化活性金属在此类承载催化剂中的含量原则上对本新型工艺成功与否并不至关重要。但是，高催化活性金属含量一般比低含量更能实现较高的时空转化率。一般地，所用的承载催化剂包含0.1～90wt％，优选0.5～40wt％的催化活性金属，基于催化剂总体。因为这些含量与催化剂总体包括载体物都有关，但是随载体物种类的不同其比重和比表面积千差万别，比这些含量低或高的值也是可能的，并不会对本新型工艺的结果造成不利影响。在特定载体物上施用大量的催化活性金属当然也是可能的。而且，催化活性金属可借比如DE-A 2 519 817、EP-A 1 77 219和EP-A 285 420的工艺施用到载体上。在上述公开物所公开的催化剂中，催化活性金属是以合金的形式存在的，其制备是，比如在以上述金属的盐或配合物浸渍之后进行热处理和/或还原。
沉淀型催化剂及承载型催化剂都可在反应开始阶段借助所含的氢原位活化，但是这些催化剂优选在使用前单独活化。
适宜的载体物一般是铝和钛的氧化物、二氧化锆、二氧化硅、粘土如蒙脱土、硅酸盐如硅酸镁或铝、沸石如ZSM-5或ZSM-10沸石以及活性炭。优选的载体物是氧化铝、二氧化钛、二氧化硅、二氧化锆和活性炭。各种载体物的混合物当然也可用作本新型工艺中所用异相催化剂的载体。本新型工艺中所用异相催化剂的例子如下：
活性炭载钴、二氧化硅载钴、氧化铝载钴、活性炭载铼、二氧化硅载铼、活性炭载铼/锡、活性炭载铼/铂、活性炭载铜、铜/二氧化硅、铜/氧化铝、亚铬酸铜、亚铬酸铜钡、铜/氧化铝/氧化锰、铜/氧化铝/氧化锌，以及DE-A 3 932 332、US-A 3,449,445、EP-A 44 444、EP-A 147 219、DE-A 3 904 083、DE-A 2 321 101、EP-A 415 202、DE-A 2 366 264、EP 0 552 463和EP-A 100 406中所公开的催化剂。
优选的催化剂包含铜、锰、钴、铬、钯、铂、钴或镍中的至少一个金属，特别优选铜、钴、钯、铂或铼。如果只将酯氢化，氢化催化剂优选包含铜。
对本新型工艺而言，对氢化反应采用何种温度和压力条件一般并没有严格的限制。
氢化反应温度一般为100～300℃而氢化反应压力一般为10～300bar。
通过计量添加也比化学计量低的量的本发明特定碱性化合物，基于引入的杂质，就能避免或至少大大延缓，一方面是酸化作用而另一方面是催化剂结构的改变。表现为催化剂的选择性增强及使用寿命延长，并且也以一种尚不十分清楚的方式提高了转化率。
从氢化反应得到的醇是比如可用作溶剂以及聚氨酯或聚酯等聚合物中间体或前体的化合物。本新型工艺就如下的实施例作进一步的说明，但并不对其构成限制。以气相色谱法分析反应产物。
实施例1
约20g/h 2-环十二烷亚基丙酸乙酯的50％乙醇溶液(从2-溴代丙酸乙酯与环十二烷制得)，也含有7ppm的卤素(证明为Cl)，在经180℃氢气流预活化的25ml CuO(70％)/ZnO(25％)/Al2O3(5％)催化剂上(铝酸钠和六水合硝酸锌(II)的水溶液与碳酸钠水溶液生成沉淀，经过滤分离出含有ZnO-和Al2O3-的沉淀产物，沉淀物在含有三水合硝酸铜(II)和六水合硝酸锌(II)的水溶液中制浆，以碳酸钠水溶液沉淀之，过滤、洗涤、干燥及煅烧得到的沉淀并将煅烧的粉末成型制片)于220℃/220bar氢化。氢化产物中2-环十二烷基丙醇(麝香味)的含量为70％(不计乙醇)。约8h后转化率约为93％(选择性75％)。然后向原料物料中混入50ppm的甲醇钠。结果是，所需产物的含量提高到约77％，而转化率达到96％(选择性80％)。
实施例2
以己二酸二甲酯和6-羟基己酸甲酯为主的混合物(按DE-A 19 607953的实施例步骤1-4制备)，在经180℃氢气流预活化的2.51Süd-Chemie制T 4489 Cu/Al/Mn催化剂上氢化(进料1kg，反应器温度205～220℃，压力250bar)。氢化原料含有约1ppm的卤素化合物(以Cl为计)。氢化反应开始时，氢化产物中副产物己二醇二醚的含量为0％。6个实验日后，就能检测到醚。到第16个实验日时，醚的含量逐渐升高到0.8％(产物中1，6-己二醇的含量为27％，己二酸二甲酯残留量为3.6％，甲酯6-羟基己酸为3.2％)。将基于氢化原料500ppm的乙醇钠溶解在甲醇中，并随后以单独进料的形式加到反应器中。再也没有醚生成了(产物中1，6-己二醇的含量为30％，己二酸二甲酯的残留量为1.1％，甲酯6-羟基己酸为2.6％)。
在不加Na的情况下操作时，氢化产物中的Mn含量为5ppm。如果有Na引入，则Mn含量就降低至小于3ppm。
Claims (9)
1.一种将羧酸、酸酐或其酯在包含或者由元素周期表6、7、8、9、10和11族以及，如果适宜的话，2、14和15族的氢化作用元素构成的异相催化剂上，在液相中于100～300℃和10～300bar催化氢化成醇的工艺，其包含向氢化反应混合物中添加基于液体氢化原料为1～3000ppm的碱性碱金属化合物或碱土金属化合物，其选择自氢氧化物、碳酸盐、羧酸盐和醇盐。
2.权利要求1的工艺，其中所用的碱性碱金属化合物是碱性的钠或钾化合物。
3.权利要求1的工艺，其中添加5～600ppm的碱性碱金属化合物或碱土金属化合物，基于液体氢化原料。
4.权利要求1的工艺，其包含将4～6个碳原子的二羧酸、酸酐或其酯氢化成相应的二醇。
5.权利要求1的工艺，其中氢化反应的氢和/或氢化反应的原料中包含卤素化合物。
6.权利要求1的工艺，其包含采用包括铜、锰、铬、钯、铂、钴或镍中至少一种元素的氢化反应催化剂。
7.权利要求1的工艺，其中氢化反应催化剂包含或由铜、钴、钯、铂或铼中的至少一种元素构成。
8.权利要求1的工艺，其包含在包括或由铜构成的催化剂的存在下氢化酯。
9.权利要求1的工艺，其包含在铜催化剂上经添加5～600ppm的碱性钠或钾化合物，将4～6个碳原子的二羧酸的酯氢化成相应的二醇。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997156171 DE19756171A1 (de) | 1997-12-17 | 1997-12-17 | Verfahren zur Hydrierung von Carbonsäuren oder deren Anhydriden oder Estern zu Alkoholen |
| DE19756171.3 | 1997-12-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281425A CN1281425A (zh) | 2001-01-24 |
| CN1170796C true CN1170796C (zh) | 2004-10-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988119765A Expired - Fee Related CN1170796C (zh) | 1997-12-17 | 1998-12-04 | 羧酸、酸酐或其酯经氢化制醇的工艺 |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1042260B1 (zh) |
| JP (1) | JP2002508342A (zh) |
| KR (1) | KR20010015877A (zh) |
| CN (1) | CN1170796C (zh) |
| CA (1) | CA2311589A1 (zh) |
| DE (2) | DE19756171A1 (zh) |
| ES (1) | ES2195440T3 (zh) |
| MY (1) | MY133071A (zh) |
| TW (1) | TW472034B (zh) |
| WO (1) | WO1999031035A1 (zh) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100546986B1 (ko) * | 1999-11-05 | 2006-01-26 | 아사히 가세이 가부시키가이샤 | 디올 혼합물의 제조 방법 |
| DE10023256A1 (de) * | 2000-05-12 | 2001-11-15 | Basf Ag | (+)-und(-)-2-Cyclododecylpropanol und (+)-und(-)-2-Cyclododecylpropionsäure sowie deren Herstellung und Verwendung |
| DE10024542A1 (de) | 2000-05-18 | 2001-11-22 | Basf Ag | Verfahren zur Herstellung von gesättigten C3-C20-Alkoholen |
| JP4034289B2 (ja) | 2004-04-02 | 2008-01-16 | 花王株式会社 | 脂肪アルコールの製造方法 |
| JP5693561B2 (ja) * | 2009-04-08 | 2015-04-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | １，６−ヘキサンジオールをオリゴ−およびポリエステルの水素化によって製造する方法 |
| DE102009047193A1 (de) | 2009-11-26 | 2011-06-01 | Basf Se | Verfahren zur Herstellung von Diolen durch Hydrierung eines Carbonsäure enthaltenden Gemisches mittels Kobalt enthaltenden Katalysatoren |
| NZ743055A (en) | 2013-03-08 | 2020-03-27 | Xyleco Inc | Equipment protecting enclosures |
| CN105435809B (zh) * | 2014-08-27 | 2018-03-20 | 中国石油化工股份有限公司 | 加氢催化剂及其制备方法和应用以及加氢反应的方法 |
| CN108707058A (zh) * | 2018-04-11 | 2018-10-26 | 华东师范大学 | 一种两步法转化生物油脂为线性α-烯烃的方法 |
| JPWO2020008617A1 (ja) * | 2018-07-06 | 2021-06-10 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | 水素化用触媒及びジオールの製造方法 |
| DE102019105105A1 (de) * | 2019-02-28 | 2020-09-03 | Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen | Verfahren zur Herstellung von 1,2-Propandiol |
| US11440863B2 (en) | 2019-06-12 | 2022-09-13 | Evonik Operations Gmbh | Process for preparing an alcohol from hydrocarbons |
| EP4197992A1 (de) | 2021-12-20 | 2023-06-21 | Evonik Operations GmbH | Verfahren zur herstellung eines alkohols und abtrennung des homogenen katalysatorsystems unter verwendung einer membran umfassend eine trennaktive schicht aus paek und einer unterstruktur, die paek umfasst |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703585A1 (de) * | 1987-02-06 | 1988-08-18 | Consortium Elektrochem Ind | Alkohole und ether mit cyclododecyl- und cyclododecenylgruppen, deren herstellung und verwendung als duftstoffe |
| GB2215330A (en) * | 1988-03-04 | 1989-09-20 | Shell Int Research | Hydrogenation of esters into alcohols |
| DD277270A1 (de) * | 1988-11-28 | 1990-03-28 | Miltitz Chem Werk | Verfahren zur hydrierung von carbonylverbindungen |
| DD281182A5 (de) * | 1989-04-10 | 1990-08-01 | Hydrierwerk Rodleben Veb | Verfahren zur herstellung von gesaettigten fettalkoholen |
| DE4127318A1 (de) * | 1991-08-17 | 1993-02-18 | Hoechst Ag | Kupfer-zinkoxid-aluminiumoxid enthaltende katalysatoren |
-
1997
- 1997-12-17 DE DE1997156171 patent/DE19756171A1/de not_active Ceased
-
1998
- 1998-11-09 TW TW87118602A patent/TW472034B/zh active
- 1998-11-20 MY MYPI98005291A patent/MY133071A/en unknown
- 1998-12-04 JP JP2000538967A patent/JP2002508342A/ja not_active Withdrawn
- 1998-12-04 KR KR1020007006583A patent/KR20010015877A/ko not_active Application Discontinuation
- 1998-12-04 ES ES98964487T patent/ES2195440T3/es not_active Expired - Lifetime
- 1998-12-04 CA CA002311589A patent/CA2311589A1/en not_active Abandoned
- 1998-12-04 DE DE59807773T patent/DE59807773D1/de not_active Expired - Lifetime
- 1998-12-04 EP EP98964487A patent/EP1042260B1/de not_active Expired - Lifetime
- 1998-12-04 WO PCT/EP1998/007900 patent/WO1999031035A1/de not_active Application Discontinuation
- 1998-12-04 CN CNB988119765A patent/CN1170796C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999031035A1 (de) | 1999-06-24 |
| TW472034B (en) | 2002-01-11 |
| ES2195440T3 (es) | 2003-12-01 |
| MY133071A (en) | 2007-10-31 |
| CN1281425A (zh) | 2001-01-24 |
| KR20010015877A (ko) | 2001-02-26 |
| EP1042260A1 (de) | 2000-10-11 |
| DE59807773D1 (de) | 2003-05-08 |
| CA2311589A1 (en) | 1999-06-24 |
| EP1042260B1 (de) | 2003-04-02 |
| JP2002508342A (ja) | 2002-03-19 |
| DE19756171A1 (de) | 1999-07-01 |
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